In the field of the art, recently, there have been the demands for the techniques capable of rapidly processing light-sensitive materials and obtaining stable photographic characteristics which are particularly excellent in processing stability and, inter alia, the demands for rapidly processable light-sensitive material developing methods.
To be more concrete, light-sensitive materials have been finished in a continuous process with an automatic processor installed in each photofinishing laboratory. However, as a part of customer-service improvements. Completion of a full series of the services within one day has been demanded, including the acceptance of an photofinishing order, the completion of the photofinishing, and the return of the finished photo articles to customers. Recently, it has urgently been demanded to develop a further rapid processing technique capable of completing the above-mentioned services within only several hours time.
Reviewing the conventional rapid processing techniques for light-sensitive materials, they are roughly classified into the following techniques:
(1) Techniques based on the improvements of light-sensitive materials: PA1 (2) Techniques based on the physical means taken in the course of development processes; and PA1 (3) Techniques based on the improvements of solution composition used in development processes.
Among the above techniques, the following have been known.
The techniques of the above classification (1) include, for example, &lt;1&gt; those based on the improvements of silver halide composition, such as a technique of making silver halide finely grained, as disclosed in Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) No. 51-77223(1976), and a technique of lowering silver bromide content of silver halide as disclosed in Japanese Patent O.P.I. Publication No. 56-18939(1981); &lt;2&gt; Those on the application of additives, such as a technique of adding 1-aryl-3-pyrazolidone having a specific structure into a light-sensitive material, as disclosed in Japanese Patent O.P.I. Publication No. 56-64339(1981), and the techniques of adding I-aryl pyrazolidone, as disclosed in Japanese Patent O.P.I. Publication Nos. 57-144547(1982), 58-50534(1983), 58-50535(1983) and 58-58-50536(1983); &lt;3&gt; those based on the application of a high-rate reactive coupler, Such as the techniques of using high-rate reactive yellow couplers, as disclosed in Japanese Patent Examined Publication No. 51-10783(1976), and Japanese Patent O.P.I. Publication Nos. 50-123342(1975) and 51-102636(1976); &lt;4&gt; those of thinning a photographic component layer, such as disclosed in Japanese Patent Application No. 60-204992(1985); and so forth.
The techniques of the above classification (2) include, for example, those of stirring a processing solution, such as that disclosed in Japanese Patent O.P.I. Publication No. 62-180369(1987), that of raising a temperature of a processing solution as disclosed in Japanese Patent O.P.I. Publication No. 62-22-2255(1987), and so forth.
The techniques of the above classification (3) include, for example, &lt;1&gt; those of using a development accelerator: &lt;2&gt; those of concentrating a color developing agent; &lt;3&gt; those of lowering the concentration of halide ions and, particularly, bromide ions; and so forth.
Among the above techniques and particularly those of Classification (1), the techniques of using a high content of silver chloride, such as disclosed in Japanese Patent O.P.I. Publication Nos. 58-95345(1983), 60-19140(1985), and 58-95736(1983), may be able to give a particularly excellent rapid-processability. For example, Eastman Kodak Company has put Ektacolor 2001 Paper and Konica Corporation has done Konica Color QA Paper each to practical application.
The present inventors have studied more rapid processing techniques by making use of principally silver chloride-containing emulsions endowed particularly with excellent rapid processability. Consequently, they have found some obstacles to achievement of rapid processing in bleach-fixing process and that color developments can be made more rapid when using a high silver chloride-containing emulsion and the above-mentioned rapid processing technique in combination. For example, the techniques of raising a temperature of a bleach-fixer has the problems that the bleach-fixer may hardly be handled because a high temperature processing cannot be avoided, or the so-called sulfuration, formation of free sulfur or sulfide. is liable to occur because the preservability of the bleach-fixer is so seriously lowered that the bleach-fixer loses its commercial value absolutely. It has also been found that a further problem, namely, reticulation, is liable to arise.
Besides the above, the techniques of increasing the concentrations of a bleacher and/or a fixer have also been known. In these techniques, a rapid processability may be achieved to some extent though, it has been found that these techniques have their limits to rapid processing functions when using the conventional silver chlorobromide emulsions which are principally silver bromide-containing emulsions. Therefore, bleaching and/or fixing functions are rather hindered from displaying and a problem of edge stain is raised.
There is a known technique of adding halogen ions as one of the other rapid processing techniques using bleach-fixers. It has been proved from the studies of the present inventors that this particular technique also has problems. For example, the halogen ions are seemingly liable to produce stains on processing apparatus, or that this technique is not so suitable for rapidly processing light-sensitive materials, particularly those principally silver chloride containing a emulsion, because a good effect may be expected unless a large amount of the halogen ions is added.
As described above, it has been very difficult in the field of the art to achieve a rapid bleach-fixing processing, as well as to achieve both of a stable bleach-fixer and the stable processing method using the bleach-fixer.
Taking the above-mentioned facts and problems into consideration, the present inventors have studied the rapid processing functions of bleach-fixers. As a result, they have discovered that the above-mentioned problems can be diminished when using a light-sensitive material comprising an emulsion highly containing silver chloride, while, in the conventional light-sensitive materials each highly containing silver bromide, the bleach-fixing function is rather lowered in a rapid processing and, particularly, in a processing carried out within 30 seconds or shorter, even if increasing the concentrations of the bleacher and/or fixer of a bleach-fixer. The present inventors have also found that the above-mentioned edge-stains produced by increasing the concentrations of the bleacher and/or fixer can be reduced by making a bleach-fixing time shorter and that, in the case of a highly silver chloride-containing emulsions, the desilvering function can be accelerated when a chloride concentrated to a certain level is present. These discoveries led the inventors to make this invention.
It may be considered from the above-mentioned facts that, in the case of using the conventional highly silver bromide-containing emulsions, a rapid processability may be achieved by increasing the concentration of a bleacher and/or fixer to a certain point of time because the rate of the bleaching and/or fixing are determined by diffusion rate of the bleaching and/or fixing agent. However, after that, the rate of bleaching and/or fixing are determined by reaction rate, therefore, the bleach-fixing property has its limit. Contrary, to this, in the case of using silver chloride emulsions, the reaction rate is not more bleaching and/or fixing rate thereof are not more determined by diffusion rate than in a highly silver bromide-containing emulsion, but almost determined by the diffusion rate.
Further, concerning the edge-stains, a reflection type light-sensitive material using a paper support, such as a color paper, is liable to the edge-stains more than those for photographing use. In addition, the edge-stains are liable to be deteriorated when using a highly concentrated bleacher and/or fixer. It has been beyond the expectations for the inventors that such edge-stains can be diminished because a processing time may be shortened by making use of a highly silver chloride-containing emulsion and that the desilvering function may be accelerated by making present a chloride concentrated to a certain level.